JP7051134B2 - Methods for Manufacturing Protected Anodes and Protected Anodes and Methods for Using Protected Anodes - Google Patents

Description

Cross-reference to related applications This application claims the priority benefit of US Provisional Patent Application No. 62 / 409,261 filed October 17, 2016, which is incorporated herein by reference in its entirety. ing.

Background of the Disclosure The Fields of the Disclosure This disclosure generally relates to batteries (or batteries). More specifically, the present disclosure relates to a protected anode (or protected anode or protected anode) for a battery, and a method for manufacturing such a protected anode for a battery.

Related Technology Descriptions Rechargeable (or rechargeable) metal-sulfur batteries (or metal-sulfer batteries), metal-air batteries (or metal-air batteries) and metal-ion batteries (or metal-ion batteries). Batteries) have shown tremendous potential as a major power source in many applications such as electric vehicles and microelectronics due to their outstanding energy density. However, the practical performance of these systems is limited by the shortening of their cycle life due to degradation of the anode electrodes.

In particular, combinations of metals such as lithium, anodes, and liquid electrolyte solutions are rechargeable due to the high reactivity of the active metal with any relevant polar aprotic solvent and / or salt anion in the electrolyte solution. It is problematic for batteries. For example, a surface reaction of a lithium metal with an electrolyte component can result in the formation of a mosaic structure of insoluble surface species at the solid electrolyte interface (SEI), causing loss of anode material. It leads to low cycling efficiency, gradual capacity loss, and poor cycling. In addition, the complex and non-uniform SEI results in a non-uniform current distribution of the lithium electrode, which can cause an internal short circuit, for example in a lithium ion battery.

Therefore, there is still a need for more robust protected anode electrodes with longer cycle life in metal-sulfur batteries, metal-air batteries, and metal-ion batteries.

Summary of the present disclosure One aspect of the present disclosure is a method for manufacturing a protected anode, which method is:
Providing an electrochemical cell (or step or step) and performing a discharge-charge cycle (or step or step)
Including
The above electrochemical cell is
A cathode comprising at least one transition metal dichalcogenide (or transition metal dichalcogenide).
Anode containing metal,
Containing electrolytes that come into contact with the transition metal dichalcogenides of the cathode and the metal of the anode, and carbon dioxide dissolved in the electrolyte (middle).
The above discharge-charge cycle is
Includes discharging the electrochemical cell and applying a voltage across the anode and cathode for sufficient time to charge the electrochemical cell.
In that method
Electrochemical cells are virtually free of water
One or more chemical species (or chemical species) are deposited (or deposited or / or deposited or deposited) on the anode (above), and this species is a discharge-charge cycle (medium). ), Which is dissolved in the electrolyte (middle).

Another aspect of the present disclosure is the method as described above, and further.
After one or more discharge-charge cycles, removing (or removing) the protective anode from the electrochemical cell (or step or step), and configuring the battery (or battery) (or step or step).
Including
The above battery is
Protective anode,
It contains an electrolyte that contacts the cathode and, if necessary, the metal of the anode.

Another aspect of the present disclosure is a protective anode, the protective anode comprising a protective layer, the protective layer being disposed on the anode, the anode being one comprising a lithium metal.
The protective layer contains Li ₂ CO ₃ , the amount of which is at least 50 atomic% of the protective layer.

Another aspect of the present disclosure is a battery (or battery), the battery comprising a protective anode as described above, further comprising an electrolyte in contact with the anode and a cathode.

As described in detail in Example 2 below, is a graph of the performance of a lithium-air battery utilizing a protective anode made according to Example 1 over 800 charge-discharge cycles. As described in more detail in Example 3 below, it is a graph showing the performance of an electrochemical cell using a protected anode made according to Example 1 as a working electrode and counter electrode throughout a high rate cycling experiment. .. 3 is a graph of the cell potentials of Example 3 over the course of a low rate deep cycling experiment performed after a high rate cycling experiment. It is a typical XPS spectrum of the surface of the protected anode prepared according to Example 1 focusing on the Li 1s region. The experiment is described in more detail in Example 4 below. It is a typical XPS spectrum of the surface of the protected anode prepared according to Example 1, focusing on the C 1s region. The experiment is described in more detail in Example 4 below. It is a typical XPS spectrum of the surface of the protected anode prepared according to Example 1 focusing on the O1s region. The experiment is described in more detail in Example 4 below. A graph of the cycle life and first cycle polarization gap of a lithium-air battery utilizing a protected anode as a function of the number of anode protection cycles performed, as described in more detail in Example 5 below. Is. As described in more detail in Example 6 below, in electrochemical impedance spectroscopy (EIS) of lithium-air batteries using protected anodes made by varying the number of anode protection cycles. be. It is a scanning electron microscope (SEM) image of the surface of the protective anode made according to Example 1 as described in more detail in Example 7 below. The scale bar is 1 μm and the inserted image width is 500 nm. It is a schematic diagram of the lithium-air battery of Example 2.

Detailed Description of the Disclosure The individual items presented herein are solely for the purpose of illustration and exemplary embodiments of the invention, and various embodiments of the invention. It is presented to provide what appears to be the form for carrying out the most useful and easy-to-understand inventions of the principles and conceptual aspects of form. In this regard, we do not attempt to provide structural details of the invention in more detail than necessary for a basic understanding of the invention, and how some embodiments of the invention are actually embodied. Drawings and / or examples revealing to those skilled in the art show embodiments for carrying out the invention. Accordingly, prior to the description of the processes and devices of the present disclosure, the embodiments described herein are not limited to a particular embodiment, device, or configuration and are therefore subject to change, of course. Please understand. It should also be understood that the terms used herein are intended to describe only certain aspects and are not intended to be limiting unless specifically defined herein.

The terms "a", "an", "the", and similar subject indications used in the context of describing the invention (especially in the context of the following claims) are set forth herein in particular. Unless otherwise or contextually clearly inconsistent, it should be interpreted as covering both singular and plural. The enumeration of a range of values herein is intended to serve merely as a concise way to individually refer to each separate value contained within that range. Unless otherwise indicated herein, each distinct value is incorporated herein as if it were individually listed herein. As used herein, the range can be expressed as "about" from one particular value and / or "about" another particular value. When such a range is represented, another embodiment includes from one particular value and / or to another particular value. Similarly, if the value is expressed as an approximation using the antecedent "about", it will be understood that that particular value forms another aspect. Each end point of the range is important in relation to the other end point and is also independent of the other end point.

All methods described herein can be performed in any suitable sequence of steps, unless otherwise indicated herein or, in context, there is no clear contradiction. The use of any example, or exemplary language (eg, "such as (etc.)") presented herein is solely intended to better clarify the invention and is otherwise patented. It does not impose any limitation on the claimed scope of the invention. No wording herein should be construed to indicate any unclaimed element that is essential to the practice of the invention.

Unless otherwise apparently necessary in the context, such as "comprise", "comprising", etc., throughout the mode and claims for carrying out the invention. A word should be interpreted in an inclusive or exhaustive sense as an antonym of an exclusive meaning, i.e., in the sense of "inclusion, but not limited to". Words that use the singular or plural also include plural and singular, respectively. In addition, terms such as "herein", "above", and "below", as well as words with similar meanings, as a whole when used in this application. It refers to this application and does not refer to any particular part of this application.

As will be appreciated by those skilled in the art, each embodiment disclosed herein can include, essentially consists of, the particular stated elements, steps, components, or components. Or it can consist of them. As used herein, the transitional terms "comprise" or "comprises", even in large quantities, are unspecified elements, steps, components, Or it means that it includes but is not limited to the components and that the inclusion of them is allowed. The transition phrase "consisting of" excludes any unspecified element, step, component, or component. The transition phrase "consisting essentially of" covers the scope of the embodiment to a particular element, step, component, or component that does not substantially affect the embodiment. limit.

Unless otherwise indicated, all numbers used herein and in the claims to represent properties such as component quantity, molecular weight, reaction conditions, etc. are, in all cases, "about". It should be understood that it is modified by the term. Accordingly, unless indicated otherwise, the numerical parameters set forth herein and in the appended claims may vary depending on the desired properties sought to be obtained by the present invention. It is an approximate value. At the very least, it does not attempt to limit the doctrine of equivalents application to the claims, and each numerical parameter is at least taken into account the number of significant digits reported and by applying ordinary rounding techniques. Should be interpreted. Where more clarity is required, the term "about" has the meaning that, when used in conjunction with a numerical value or range of indication, is naturally considered by one of ordinary skill in the art to belong to it, ie. Displayed value ± 20%, displayed value ± 19%, displayed value ± 18%, displayed value ± 17%, displayed value ± 16%, displayed value ± 15%, displayed value ± 14%, displayed ± 13% of the value, ± 12% of the displayed value, ± 11% of the displayed value, ± 10% of the displayed value, ± 9% of the displayed value, ± 8% of the displayed value, ± 7% of the displayed value, the displayed value ± 6% of the displayed value, ± 5% of the displayed value, ± 4% of the displayed value, ± 3% of the displayed value, ± 2% of the displayed value, or within the range of ± 1 of the displayed value, from the displayed value or range. It means a little more or a little less.

Although the numerical ranges and parameters indicating the broad range of the present invention are approximate values, the numerical values shown in the particular examples are reported as accurately as possible. However, each number essentially contains a certain error that inevitably arises from the standard deviation found in their respective test measurements.

The grouping of alternative elements or embodiments of the invention disclosed herein should not be construed as limiting. Each group member may be referred to and claimed individually or in any combination with other members or elements of the group as seen herein. It is expected that one or more members of a group may be included in or removed from the group for convenience and / or for patent requirements. In the event of any such inclusion or deletion, the specification includes the group as amended and thus satisfies the written description of all Markush groups used in the appended claims. Is considered.

Several embodiments of the invention are described herein, including the best known embodiments of the invention. Of course, modifications to these described embodiments will be apparent to those of skill in the art upon reading the above description. The present inventors expect that those skilled in the art will appropriately adopt such a modified form, and the present inventors carry out the present invention in addition to those specifically described in the present specification. Is intended to be. Accordingly, the invention includes, as permitted by applicable law, all modifications and equivalents of the subject matter of the invention listed in the claims herein. Moreover, any combination of the above elements in all of those possible variants is included in the invention unless otherwise indicated herein or in the context of which is clearly inconsistent.

Also, each of the cited references and printed publications with which references are made to patents and printed publications throughout the specification are individually incorporated herein by reference in their entirety.

Finally, it should be understood that the embodiments of the invention disclosed herein illustrate the principles of the invention. Other modifications that may be adopted are within the scope of the present invention. Thus, as an example, but not limited to, alternative configurations of the invention may be utilized as taught herein. Therefore, the invention is not limited to exactly as illustrated and described.

In various embodiments and embodiments, the present disclosure comprises discharging and charging a cathode containing at least one transition metal dichalcogenide, an anode containing a metal, an electrolyte, and an electrochemical cell containing oxygen dioxide dissolved in the electrolyte. Regarding the protective anode produced. The present disclosure demonstrates that such a protective anode does not adversely affect battery performance while maintaining a significantly improved cycle life.

One aspect of the present disclosure is a method of making a protective anode. This method comprises a cathode containing at least one transition metal dichalcogenide, an anode containing the metal, an electrolyte in contact with the transition metal dichalcogenide of the cathode and the metal of the anode, and carbon dioxide dissolved in the electrolyte. Includes providing chemical cells. The method comprises performing a discharge-charge cycle, which comprises discharging the electrochemical cell and applying a voltage across the anode and cathode for a time sufficient to charge the electrochemical cell. One or more species formed in the discharge-charge cycle and dissolved in the electrolyte deposit (or deposit or deposit) on the anode. The electrochemical cell of this method is substantially water free.

In certain embodiments, the electrochemical cell is less than 5% by weight, eg, less than 4.5% by weight, or less than 4% by weight, or less than 3.5% by weight, or less than 3% by weight, or 2 of the electrolyte. .Contains less than 5% by weight, or less than 2% by weight, or less than 1.5% by weight, or less than 1% by weight, or less than 0.75% by weight, or less than 0.5% by weight.

In certain embodiments of the methods described separately herein, the electrochemical cell is substantially free of H ₂ and O ₂ . In certain embodiments, the electrochemical cell is in an amount of less than about 5% by weight of the electrolyte, eg, less than about 4% by weight, or less than about 3% by weight, or less than about 2% by weight, or less than about 1% by weight of the electrolyte. Including H ₂ of. In certain embodiments, the electrochemical cell is in an amount of less than about 5% by weight of the electrolyte, eg, less than about 4% by weight, or less than about 3% by weight, or less than about 2% by weight, or less than about 1% by weight of the electrolyte. Includes O ₂ of. In certain embodiments, the electrochemical cell is less than about 10% by weight of the electrolyte, eg, less than about 9% by weight, or less than about 8% by weight, or less than about 7% by weight, or less than about 6% by weight, or Includes combined amounts of less than about 5% by weight, or less than about% by weight, or less than about 3% by weight, less than about ₂ % by weight, or less _than about 1% by weight.

In certain embodiments of the methods described separately herein, the method further comprises one or more additional discharge-charge cycles. In certain embodiments, the total number of discharge-charge cycles is 2-25, eg, 2-24, or 2-23, or 2-22, or 2-21, or 2-21, or 2-20, or. 2-19, or 2-19, or 2-18, or 2-17, or 2-16, or 2-16, or 2-15, or 2-14, or 2-13, or 2-12, or 2-11, or 2-10, or 2-9, or 2-8, or 2-7, or 2-6, or 2-5, or 3-25, or 4-25, or 5-25, or 6-25, or 7-25, or 8-25, or 9-25, or 10-25, or 11-25, or 12-25, or 13-25, or 14-25, or 15-25, or 16-25, or 17-25, or 18-25, or 19-25, or 20-25, or 3-24, or 4-23, or 5-22, or 5-21, or 5-20, or 5-19, or 5-18, or 5-17, or 5-16, or 5-15, or 6-14, or 7-13, or 8-12, or 9-11.

In certain embodiments of the methods described separately herein, the applied voltage is from about 1V to about 5V, such as about 1.25V to 4.75V, or about 1.5V to 4.5V, or about 1. It is in the range of .75V to 4.25V, or 2V to 4V, or 2.25V to 3.75V, or 2.5V to 3.5V, or the voltage is about 1.5V, or about 1.75V. Or about 2V, or about 2.25V, or about 2.5V, or about 2.75V, or about 3V, or about 3.25V, or 3.5V, or about 3.75V, or about 4V, or about 4 It is .25V, or about 4.5V.

As mentioned above, in the methods and devices of the present disclosure, the anode comprises a metal. As one of ordinary skill in the art will understand, various structures can be used for the anode. The anode can be, for example, essentially metal (eg, as a rod, plate, or other shape). In other embodiments, the anode may be formed from a metal alloy, or a metal deposit (or deposit or deposit) on a substrate (eg, a substrate formed from a different metal or from another conductive material). It may be formed as a deposit. Other metals, including those in their zero valence state, may be used, as will be appreciated by those skilled in the art. For example, in certain embodiments, the metal can be provided as part of a composite metal oxide or carbonaceous material from which the metal can be reduced to provide metal ions and one or more electrons.

As mentioned above, in the methods and devices of the present disclosure, the anode may contain metal and may be formed, for example, as a rod, plate, chip, disk or the like. Those skilled in the art will appreciate that the anode may have a variety of different dimensions, eg, chips with thicknesses such as 0.15 mm, 0.25 mm, 0.5 mm, 0.65 mm. ..

Lithium is often used as the anodic metal, but other embodiments of the present disclosure are directed to other anodic metals described herein. Accordingly, the embodiments relating to lithium herein for carrying out the invention are merely examples, and in other embodiments of the present disclosure, in place of and / or in addition to lithium, the present specification. Other metals may be used, including those described in. Suitable metals for use in the anodes of the present disclosure include alkali metals such as lithium, sodium and potassium, alical earth metals such as magnesium and calcium, Group 13 elements such as aluminum, transitions such as zinc, iron and silver. Metals, as well as alloying materials containing any of these metals, or materials containing any of these metals are included, but are not limited to. In certain embodiments, the metal is selected from one or more of lithium, magnesium, zinc, and aluminum. In another particular embodiment, the metal is lithium.

When lithium is used as the metal of the anode, a lithium-containing carbonaceous material, an alloy containing a lithium element, or a composite oxide of lithium, a nitride, or a sulfide may be used. Examples of alloys containing the element lithium include, but are not limited to, lithium-aluminum alloys, thirium-tin alloys, lithium-lead alloys, and lithium-silicon alloys. Examples of lithium-containing composite metal oxides include lithium titanium oxide. Examples of lithium-containing composite metal nitrides include lithium cobalt nitrides, lithium iron nitrides, and lithium manganese nitrides.

As mentioned above, in the methods and devices of the present disclosure, the cathode comprises at least one transition metal dicalcogenide. Examples of transition metal dicalcogenides are selected from the group consisting of TiX ₂ , VX ₂ , CrX ₂ , ZrX ₂ , NbX ₂ , MoX ₂ , HfX ₂ , WX ₂ , TaX ₂ , TcX ₂ , and ReX ₂ . Is included, where X is independently S, Se, or Te. In one embodiment, each transition metal dicalcogenide is selected from the group consisting of TiX ₂ , MoX ₂ , and WX ₂ , where X is independently S, Se, or Te. In another embodiment, each transition metal dicalcogenide is selected from the group consisting of TiS ₂ , TiSe ₂ , MoS ₂ , MoSe ₂ , WS _2, and WSe ₂ . For example, in one embodiment, each transition metal dicalcogenide is TiS ₂ , MoS ₂ , or WS ₂ . In another embodiment, each transition metal dicalcogenide is MoS ₂ or MoSe ₂ . In one embodiment, the transition metal dicalcogenide may be MoS ₂ .

The at least one transition metal dicalcogenide itself can be provided in various forms, for example as a bulk material, in nanostructured form, as an aggregate of particles, and / or as an aggregate of supporting particles. As will be appreciated by those skilled in the art, transition metal dicalcogenides in the form of bulk may have a layered structure typical of such compounds. Transition metal dicalcogenides are monolayers (or monolayers), nanotubes, nanoparticles (or nanoparticles), nanoflakes (eg, multi-layer nanoflakes), nanosheets, nanoribbons, It may have a nanostructured morphology including, but not limited to, nanoporous solids and the like. As used herein, the term "nanostructure" refers to dimensions in the nanometer range (ie, greater than 1 nm and less than 1 μm) (eg, of pores, thickness, diameter, as appropriate for the structure). Refers to materials with dimensions). In some embodiments, the transition metal dichalcogenide is a layered laminated bulk transition metal dichalcogenide with metal atom termination edges (eg, MoS ₂ with molybdenum termination edges). In other embodiments, transition metal dicalcogenide nanoparticles (eg, MoS ₂ nanoparticles) may be used in the devices and methods of the present disclosure. In other embodiments, transition metal dicalcogenide nanoflakes (eg, MoS ₂ nanoflakes) may be used in the devices and methods of the present disclosure. Nanoflakes are, for example, each of which is incorporated herein by reference in its entirety, Coleman, J. Mol. N. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science331, 568-71 (2011), and Yasai, P. et al. High-Quality Black Phosphorus Atomic Layers by Liquid-Phase Exfoliation by et al. Adv. Mater. It can be made by liquid exfoliation as described in (2015) (doi: 10.1002 / adma. 2014005150). In other embodiments, transition metal dicalcogenide nanoribbons (eg, MoS ₂ nanoribbons) may be used in the devices and methods of the present disclosure. In other embodiments, TMDC nanosheets (eg, MoS ₂ nanosheets) may be used in the devices and methods of the present disclosure. One of ordinary skill in the art can select the appropriate form for a particular device.

In certain embodiments of the methods described separately herein, transition metal dicalcogenide nanostructures (eg, nanoflakes, nanoparticles, nanoribbons, etc.) have an average size (or average size) of about 1 nm and 1000 nm. ). The size associated with nanoparticles is their maximum diameter. The size associated with the nanoflakes is its maximum width along its main surface. The size associated with the nanoribbon is the width of the entire ribbon. The size associated with nanosheets is their thickness. In some embodiments, the transition metal dicalcogenide nanostructures are about 1 nm to about 400 nm, or about 1 nm to about 350 nm, or about 1 nm to about 300 nm, or about 1 nm to about 250 nm, or about 1 nm to about 200 nm, or About 1 nm to about 150 nm, or about 1 nm to about 100 nm, or about 1 nm to about 80 nm, or about 1 nm to about 70 nm, or about 1 nm to about 50 nm, or 50 nm to about 400 nm, or about 50 nm to about 350 nm, or about 50 nm. ~ About 300 nm, or about 50 nm to about 250 nm, or about 50 nm to about 200 nm, or about 50 nm to about 150 nm, or about 50 nm to about 100 nm, or about 10 nm to about 70 nm, or about 10 nm to about 80 nm, or about 10 nm to About 100 nm, or about 100 nm to about 500 nm, or about 100 nm to about 600 nm, or about 100 nm to about 700 nm, or about 100 nm to about 800 nm, or about 100 nm to about 900 nm, or about 100 nm to about 1000 nm, or about 400 nm to about. It has an average size of 500 nm, or about 400 nm to about 600 nm, or about 400 nm to about 700 nm, or about 400 nm to about 800 nm, or about 400 nm to about 900 nm, or about 400 nm to about 1000 nm. In certain embodiments, the transition metal dicalcogenide nanostructures have an average size of about 1 nm to about 200 nm. In some other embodiments, the transition metal dicalcogenide nanostructures have an average size of about 1 nm to about 400 nm. In certain other embodiments, the transition metal dicalcogenide nanostructures have an average size of about 400 nm to about 1000 nm. In certain embodiments, the transition metal dicalcogenide nanostructures are nanoflakes with an average size of about 1 nm to about 200 nm. In certain other embodiments, the transition metal dicalcogenide nanoflakes have an average size of about 1 nm to about 400 nm. In certain other embodiments, the transition metal dicalcogenide nanoflakes have an average size of about 400 nm to about 1000 nm.

In certain embodiments of the methods described separately herein, transition metal dicalcogenide nanoflakes have an average thickness (or average thickness) of about 1 nm to about 100 μm (eg, about 1 nm to about 10 μm). , Or about 1 nm to about 1 μm, or about 1 nm to about 1000 nm, or about 1 nm to about 400 nm, or about 1 nm to about 350 nm, or about 1 nm to about 300 nm, or about 1 nm to about 250 nm, or about 1 nm to about 200 nm. Or about 1 nm to about 150 nm, or about 1 nm to about 100 nm, or about 1 nm to about 80 nm, or about 1 nm to about 70 nm, or about 1 nm to about 50 nm, or about 50 nm to about 400 nm, or about 50 nm to about 350 nm, or About 50 nm to about 300 nm, or about 50 nm to about 250 nm, or about 50 nm to about 200 nm, or about 50 nm to about 150 nm, or about 50 nm to about 100 nm, or about 10 nm to about 70 nm, or about 10 nm to about 80 nm, or about. 10 nm to about 100 nm, or about 100 nm to about 500 nm, or about 100 nm to about 600 nm, or about 100 nm to about 700 nm, or about 100 nm to about 800 nm, or about 100 nm to about 900 nm, or about 100 nm to about 1000 nm, or about 400 nm. ~ About 500 nm, or about 400 nm to about 600 nm, or about 400 nm to about 700 nm, or about 400 nm to about 800 nm, or about 400 nm to about 900 nm, or about 400 nm to about 1000 nm, and a main surface of about 20 nm to about 100 μm ( Or average dimentions (eg, about 20 nm to about 50 μm, or about 20 nm to about 10 μm, or about 20 nm to about 1 μm, or about 50 nm) along the major surface. ~ About 100 μm, or about 50 nm to about 50 μm, or about 50 nm to about 10 μm, or about 50 nm to about 1 μm, or about 100 nm to about 100 μm, or about 100 nm to about 50 μm, or about 100 nm to about 10 μm, or about 100 nm to It has an average dimension along the main surface of about 1 μm), and the aspect ratio (maximum major dimension: thickness) of the nanoflakes is, for example, at least about 5: 1 and at least about 10 on average. 1, again Can be at least about 20: 1. For example, in one embodiment, the transition metal dicalcogenide nanoflakes have an average thickness in the range of about 1 nm to about 1000 nm (eg, about 1 nm to about 100 nm), an average dimension along a main surface of about 50 nm to about 10 μm. , And have an aspect ratio of at least about 5: 1.

Those skilled in the art will recognize that at least one transition metal dicalcogenide of the cathode may be provided in various forms as long as it is in contact with the electrolyte. For example, the transition metal dicalcogenide can be placed on the substrate. For example, the transition metal dicalcogenide can be placed on a porous member (or porous member) (above), thereby diffusing a gas (eg, CO ₂ ) through the member to TMDC. be able to. The porous member may be conductive (or electrically electrically conductive). If the porous member is not conductive, one of ordinary skill in the art can arrange the electrical connection of the cathode to be made to the other part of the cathode. The substrate may be selected to allow CO ₂ to be absorbed into the device in significant amounts and transferred to the TMDC. Examples of the porous material of the substrate include carbon-based materials such as carbon black (for example, Ketjen black, acetylene black, channel black, furnace black, mesoporous carbon), activated carbon, and carbon fiber, in addition to carbon. In one embodiment, a carbon material with a large specific surface area is used. A material having a pore volume of about 1 mL / g can be used. In another case, the cathode mixes TMDC with a conductive material (eg, SUPER P brand carbon black) and a binder (eg, PTFE), followed by a current collector (or current collector) (. For example, it can be made by coating on an aluminum mesh). The proportions of these elements can usually vary. In various embodiments, the TMDC-containing cathode material (eg, the material coated on the current collector) is at least 10% by weight, at least 20% by weight, at least 50% by weight, at least 70% by weight, 10-99% by weight. %, 20-99% by weight, 50-99% by weight, 10-95% by weight, 20-95% by weight, 50-95% by weight, 10-70% by weight, 20-70% by weight, 40-70% by weight, Or it contains 70-99% by weight. In certain embodiments, it can be 95% by weight TMDC, 4% by weight PTFE binder and 5% by weight Super P, or 50% by weight TMDC, 40% by weight PTFE binder and 10% by weight Super. Can be P.

The TMDC-containing material can be coated on the current collector or porous member at any convenient thickness, for example up to 1000 μm. It is desirable that the entire cathode have some porosity so that CO ₂ can be provided to the TMDC material.

Those skilled in the art will be able to optimize the amount of TMDC present in the gas diffusing material present at the cathode.

As mentioned above, in the devices and methods of the present disclosure, the electrolyte comprises at least 1% ionic liquid. Those skilled in the art will also recognize that the term "ionic liquid" refers to an ionic material (ie, a combination of cations and anions) that is liquid at standard temperatures and pressures (25 ° C., 1 atmosphere). In certain embodiments, the ionic liquid is a compound containing at least one positively charged nitrogen, sulfur, or phosphorus group (eg, phosphonium or quaternary amine). In certain embodiments, the electrolyte comprises at least 10%, at least 20%, at least 50%, at least 70%, at least 85%, at least 90%, or even at least 95% ionic liquid.

Specific examples of ionic liquids include acetylcholine, alanine, aminoacetonitrile, methylammonium, arginine, aspartic acid, threonine, chloroformamidinium, thiouronium, quinolinium, pyrrolidinol, serinol, benzamidine, sulfamate, acetate, acetate, acetate, carbamate. Inflate, and one or more salts of cyanide, but not limited to. Those skilled in the art will select salts that are in liquid form at standard temperature and pressure. These examples are for illustration purposes only and are not meant to limit the scope of this disclosure.

In some embodiments, the ionic liquids of the present disclosure are 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-. Methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, or 1-butyl-3-methylimidazolium trifluoromethanesulfonate With imidazolium salts such as 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, or 1-butyl-1-methylpyrrolidinium. Pyrrolidinium salts such as trifluoromethanesulfonate and 1-butyl-1-methylpiperidinium tetrafluoroborate, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, or 1-butyl-1-methylpi Piperidinium salts such as peridinium trifluoromethanesulfonate and ammonium salts such as amyltriethylammonium bis (trifluoromethanesulfonyl) imide or methyltri-n-octylammoniumbis (trifluoromethanesulfonyl) imide and 1-ethyl-3-methylpyridinium. It may be a pyridinium salt such as bis (trifluoromethanesulfonyl) imide.

In certain embodiments, the ionic liquids of the present disclosure are imidazolium (class), pyridinium (class), pyrrolidinium (class), phosphonium (class), ammonium (class), sulfonium (class), prolinate (class) (or proline). It includes, but is not limited to, salts of the salts (prolinates), and methioninates (s) (or methioninates). Suitable anions for forming salts with cations include C1 _- C6 alkyl sulphates, _tosilates , methanesulfonates, bis (trifluoromethylsulfonyl) imides, hexafluorophosphates, tetrafluoroborates, triflate, halides ( Or halides), carbamate, and sulfamate are included. In certain embodiments, the ionic liquid can be a salt of a cation selected from those exemplified below.

In the formula, R ₁ to R ₁₂ are hydrogen, -OH, linear aliphatic C ₁ -C ₆ groups, branched aliphatic C ₁ -C ₆ groups, cyclic aliphatic C ₁ -C ₆ groups, -CH ₂ OH. , -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CHOHCH ₃ , -CH ₂ COH, -CH ₂ CH ₂ COH, and -CH ₂ COCH ₃ independently selected from the group. To.

In certain embodiments, the ionic liquid of the methods and devices of the present disclosure is an imidazolium salt having the following formula:

In the formula, R ₁ , R ₂ and R ₃ are independent of the group consisting of hydrogen, linear aliphatic C ₁ -C ₆ groups, branched aliphatic C ₁ -C ₆ groups, and cyclic aliphatic C ₁ -C ₆ groups. Is selected.
In other embodiments, R ₂ is hydrogen and R ₁ and R ₃ are independently selected from linear or branched C1 _{- C4} alkyl.
In certain embodiments, the ionic liquids of the present disclosure are 1-ethyl-3-methylimidazolium salts.
In another embodiment, the ionic liquid of the present disclosure is 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF ₄ ).

In general, one of ordinary skill in the art can determine whether a given ionic liquid is a co-catalyst for a reaction (R) catalyzed by TMDC as follows.
(A) A standard three-electrode electrochemical cell is filled with an electrolyte commonly used for reaction R. Common electrolytes include 0.1 M sulfuric acid and the like, or 0.1 M KOH in water and the like can also be used.
(B) The TMDC is attached to a 3-electrode electrochemical cell and a suitable counter electrode.
(C) Perform several CV cycles to clean the cell.
(D) The reversible hydrogen electrode (RHE) potential in the electrolyte is measured.
(E) The cell is filled with a reactant for reaction R, and the CV of reaction R is measured by paying attention to the potential of the peak associated with reaction R.
(F) The VI, which is the difference between the starting potential of the peak associated with the reaction and RHE, is calculated.
(G) Calculate VIA, which is the difference between the maximum potential of the peak associated with the reaction and RHE.
(H) Add 0.0001 to 99.9999% by weight of an ionic liquid to the electrolyte.
(I) RHE in reaction with an ionic liquid is measured.
(J) Focusing on the potential of the peak associated with reaction R, the CV of reaction R is measured again.
(K) Calculate V2, which is the difference between the starting potential of the peak associated with the reaction and RHE.
(L) Calculate V2A, which is the difference between the maximum potential of the peak associated with the reaction and RHE.
For ionic liquids of any concentration (eg 0.0001-99.9999% by weight), if V2 <V1 or V2A <VIA, the ionic liquid is a co-catalyst for the reaction.

In some embodiments, the ionic liquid is about 50% to about 100% by weight, or about 50% to about 99% by weight, or about 50% to about 98% by weight, or about 50% by weight of the aqueous solution. ~ 95% by weight, or about 50% by weight to about 90% by weight, or about 50% by weight to about 80% by weight, or about 50% by weight to about 70% by weight, or about 50% by weight to about 60% by weight, Alternatively, about 80% by weight to about 99% by weight, about 80% by weight to about 98% by weight, or about 80% by weight to about 95% by weight, or about 80% by weight to about 90% by weight, or about 70% by weight to about 70% by weight. Within the range of 99% by weight, about 70% by weight to about 98% by weight, or about 70% by weight to about 95% by weight, or about 70% by weight to about 90% by weight, or about 70% by weight to about 80% by weight. , Or about 50% by weight, or about 70% by weight, or about 80% by weight, or about 90% by weight, or about 95% by weight, or about 96% by weight, or about 97% by weight, or about 98% by weight, or It is present in the electrolyte in an amount of about 99% by weight. In certain embodiments, the ionic liquid is present in the electrolyte in the range of about 75% by weight to about 100% by weight, or about 90% by weight to about 100% by weight. In some other embodiments, the ionic liquid is present in the electrolyte in an amount of about 90% by weight. In other embodiments, the electrolyte consists essentially of an ionic liquid.

In certain embodiments, the electrolyte may further comprise a solution bound to at least one of a solvent, a buffer, an additive to a component of the system, or a catalyst in the system. In certain embodiments, the electrolyte may include an aprotic organic solvent. Some suitable solvents include dioxolane, dimethyl sulfoxide (DMSO), diethyl ether, tetraethylene glycol dimethyl ether (TEGDME), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate. (EMC), ethylene carbonate (EC), propylene carbonate (PC), tetrahydrofuran (THF), butylene carbonate, lactone, ester, glyme, sulfoxide, sulfoxide, polyethylene oxide (PEO), and polyacrylonitrile (PAN) alone. Alternatively, it is included in any combination, but is not limited to these. In certain embodiments, the nonionic liquid organic solvent is less than about 40% by weight, less than about 30% by weight, less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, or about 1% by weight. Even less than are present in those quantities. In certain embodiments, the electrolyte is a substantially free nonionic liquid organic solvent.

In certain embodiments, the electrolyte may further comprise other species such as acids, bases, and salts. In certain embodiments, the electrolyte may include metal ions such as lithium ions, magnesium ions, zinc ions, aluminum ions and the like. In one embodiment, the electrolyte may include lithium ions. In certain embodiments, the electrolyte may contain a salt of the metal of the anode (eg, if the anode contains lithium metal, the electrolyte is lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate. , Lithium triflate, lithium hexafluoroarsenate and other lithium salts may be included). In certain embodiments, the metal salt of the anode is present in concentrations ranging from about 0.005M to about 5M, about 0.01M to about 1M, or about 0.02M to about 0.5M. Inclusion of such other species will be apparent to those of skill in the art and is not meant to limit the scope of the present disclosure, depending on the desired electrochemical and physicochemical properties of the electrolyte.

As mentioned above, in the devices and methods of the present disclosure, the electrochemical cell comprises carbon dioxide dissolved in the electrolyte. In certain embodiments, carbon dioxide is at least about 5%, for example, at least about 7.5%, or at least about 10%, or at least about 12.5%, or at least about 15% of the saturated concentration of carbon dioxide in the electrolyte. %, Or at least about 17.5%, or at least about 20%, or at least about 22.5%, or at least about 25%, or at least about 30%, or at least about 35%, or at least about 40%, or at least. About 45%, or at least about 50%, or at least about 55%, or at least about 60%, or at least about 65%, or at least about 70%, or at least about 75%, or at least about 80%, or at least about 85. %, Or at least about 90%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99% in the electrolyte.

In certain embodiments, the method removes the protected anode from the electrochemical cell after one or more discharge-charging cycles and contacts the protected anode, cathode, and anode, and optionally the metal of the anode. Further comprising constructing a battery, comprising an anode.

Another aspect of the disclosure is a protective anode made by the method described separately herein.

Another aspect of the present disclosure is a protective anode comprising a protective layer disposed on an anode containing lithium metal, the protective layer comprising an amount of Li ₂ CO ₃ in an amount of at least 50 atomic% of the protective layer. In some embodiments, the protective layer is about 5 nm to about 5 μm, such as about 5 nm to about 40 μm, or about 5 nm to about 30 μm, or about 5 nm to about 20 μm, or about 5 nm to about 10 μm, or about 5 nm to. About 9 μm, or about 5 nm to about 8 μm, or about 5 nm to about 7 μm, or about 5 nm to about 6 μm, or about 5 nm to about 5 μm, or about 5 nm to about 4 μm, or about 5 nm to about 3 μm, or about 5 nm to about. 2 μm, or about 5 nm to about 1 μm, or about 5 nm to about 900 nm, or about 5 nm to about 800 nm, or about 5 nm to about 700 nm, or about 5 nm to about 600 nm, or about 5 nm to about 500 nm, or about 5 nm to about 450 nm. , Or about 5 nm to 400 nm, or about 5 nm to about 350 nm, or about 5 nm to about 300 nm, or about 5 nm to about 250 nm, or about 5 nm to about 200 nm, or about 10 nm to about 5 μm, or 15 nm to about 5 μm, or about. 20 nm to about 5 μm, or about 25 nm to about 5 μm, or about 50 nm to about 5 μm, or about 75 nm to about 5 μm, or about 100 nm to about 5 μm, or about 150 nm to about 5 μm, or about 200 nm to about 5 μm, or about 250 nm. Approximately 5 μm, or approximately 300 nm to approximately 5 μm, or approximately 350 nm to approximately 5 μm, or approximately 400 nm to approximately 5 μm, or approximately 450 nm to approximately 5 μm, or approximately 500 nm to approximately 5 μm, or approximately 600 nm to approximately 5 μm, or 700 nm to approximately. 5 μm, or about 800 nm to about 5 μm, or about 900 nm to about 5 μm, or about 1 μm to about 5 μm, or about 1.25 μm to about 5 μm, or about 1.5 μm to about 5 μm, or about 1.75 μm to about 5 μm, Alternatively, it has a thickness in the range of about 2 μm to about 5 μm, or about 2.25 to about 5 μm, or about 2.5 μm to about 5 μm.

Another aspect of the present disclosure is a protected anode made by the method described herein or by the methods described herein, a cathode and its anode, and optionally an electrolyte that comes into contact with the metal of the anode. , A battery.

For those skilled in the art, the battery may be any battery in which the protective anode made by the method described herein is suitable, eg, a metal-sulfur battery, a metal-air battery, or a metal-ion battery. Will be understood. In certain embodiments, the battery is a metal-air battery. In certain embodiments, the battery is a metal-air battery and the cathode comprises at least one transition metal dicalcogenide. For example, in one embodiment, the battery is the metal-air battery described in WO2016 / 100204. In other embodiments, the cathode of the battery is free of transition metal dicalcogenides. In certain embodiments, the battery is a metal-air battery and the electrolyte comprises at least 50% by weight of ionic liquid. In certain embodiments, the battery cell comprises an electrochemical cell of the method of making a protective anode, which is separately described herein, in an amount of water, H ₂ and / or greater _than the amount of O ₂ . , And / or O ₂ .

The following examples illustrate certain embodiments of the invention and their various uses. They are shown for explanatory purposes only and should not be taken as limiting the invention.

Example 1
Protecting Anode A Protected Anode was made by including a Protected Anode within an electrochemical battery cell that also contains a MoS ₂ nanoflake cathode and electrolyte.

Cathode Preparation MoS ₂ nanoflake using a liquid stripping method in which 300 mg of MoS ₂ powder (99%, Sigma-Aldrich) is dispersed in 60 mL of isopropyl alcohol (IPA) (> 99.5%, Sigma-Aldrich). Was synthesized. The solution was then exfoliated for 30 hours and centrifuged for 1 hour to extract nanoflakes from the unexfoliated powder. Dynamic Light Scattering (DLS) analysis showed a uniform size distribution of synthetic MoS ₂ nanoflake over a narrow range of 110-150 nm with an average flake size of 135 nm. MoS ₂ nanoflake (0.2 mg) coated on a conductive substrate of a gas diffusion layer (GDL: Gas Diffusion Layer) (0.2 mm thick, 80% porosity, fuel cell, etc.) with a surface area of 1 cm ^-2 . bottom. The prepared cathode was dried in a vacuum oven at 85 ° C. for 24 hours to stabilize the cathode and remove impurities. This procedure yielded a similarly prepared cathode sample with a consistent catalyst filling of 0.2 mg / cm ^-2 on the GDL substrate.

Anode Preparation A protected anode was made from a pure lithium chip with a thickness of 0.25 mm (> 99.9%, Sigma Aldrich).

Preparation of Electrolyte 0.1M Lithiumbis (Trifluoromethanesulfonyl) Imid (LiTFSI) (> 99.0%, Sigma-Aldrich), 25% 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM BF4) (HPLC) ,> 99.0, Sigma-Aldrich) and 75% dimethyl sulfoxide (DMSO) (Sigma-Aldrich) to make an electrolyte solution.

Battery Cell Fabrication All battery systems were assembled in an argon (Ar) filled glove-box with a custom Swagelok battery mechanism. This mechanism included a cathode, an anode, and three drops of electrolyte. A glass microfiber filter was used as a separator to prevent direct contact between the cathode and the anode.

Anode protection procedure (or treatment)
The assembled battery cells were first purged with pure CO ₂ (99.99%, Praxair Inc.) to remove gas impurities and prevent parasitic reactions. Next, a CO ₂ -filled battery was connected to a potentiostat (MTI Corporation) for cycling measurements. A constant current of 0.1 mA / cm ^-1 was applied in 10 consecutive cycles, each cycle consisting of a 1 hour charging process followed by a 1 hour discharging process. In-situ measurements of voltage as a function of time and capacity were recorded.

Example 2
Performance of Lithium-Air Battery with Protected Anode The protected anode made according to Example 1 is incorporated into a lithium-air battery configured as shown in FIG. 10, where the protected anode and cathode are wetted with an electrolyte. It was separated by a glass fiber filter. Cathodes and electrolytes were made according to Example 1. The assembled battery is first subjected to ~ 21% oxygen (O ₂ ), ~ 79% nitrogen (N ₂ ), 500 ppmCO ₂ and 45% relative humidity (RH) to remove gas impurities and prevent parasitic reactions. ) Was purged with an air mixture. The air mixture was a custom order (Praxair Inc.) with an accuracy of ± 1% for CO ₂ and ± 0.02% for O ₂ . Moisture was added to the gas stream prior to introduction into the battery. During the purge, sensors (Silicon Labs SI 700 x) tracked the RH and temperature of the air flow to maintain RH at 45% and temperature at 25 ° C ± 1 ° C (room temperature). Rhesus and temperature vs. time were recorded continuously (Si700x evaluation software). A lithium-air battery was connected to a potentiostat for cycling measurements. A constant current of 0.1 mA / cm ^-1 was applied in 800 cycles, each cycle consisting of a 1 hour charging process followed by a 1 hour discharging process. In-situ measurements of voltage as a function of cycle count and capacitance were recorded (see Figure 1). Throughout 800 cycles, the variation in battery performance was negligible. These results showed an increase in the number of cycles in which the polarization gap across the battery utilizing the bare lithium anode did not change by more than an order of magnitude without any adverse effect on the overall performance of the battery.

Example 3
Coulomb efficiency (or Columbia efficiency) of the protective anode
The Coulombic efficiency (or Columbic efficiency) of the protected anode was tested by high speed cycling followed by thorough removal of the anode. To make the cell, two lithium anodes with an initial theoretical capacity of Q ₀ = 10.2 mAh / cm ² were separately protected according to Example 1. The protective anode is then incorporated into the 2016 coin cell as a working electrode and counter electrode using a glassy fiber separator and an electrolyte containing 25% / 75% ionic liquid / DMSO containing 0.1 M LiTFSI. is.

High rate cycling (or high rate cycling)
The cells were subjected to a specific number of cycles (N = 51 cycles), and each cycle consisted of a 1-hour charging process followed by a 1-hour discharging process in which a current density of 2 mA / cm ² was applied. As a result, a cycle capacity of Q _c = 2 mAh / cm ² was obtained. During the discharge, 19.6 wt% lithium of the working electrode was transferred to the counter electrode. During charging, the same amount of lithium returned to the working electrode. The amount of lithium reciprocating between the working electrode and the counter electrode remains the same throughout the cycling experiment.These results shown in FIG. 2 indicate that the accumulation of lithium in the counter electrode may reduce the Coulomb efficiency of the system. Because of that, it is ideal.

Low rate deep cycling (or low rate deep cycling)
After the high rate cycling experiment, a low rate deep cycling experiment was performed on the working electrode. In cycling experiments to minimize deformation of the lithium dendrite growth and solid electrolyte interface (SEI) (ie, the interface between the lithium electrode and the electrolyte) when a current density of 0.5 mA / cm ² was applied. 4 times lower than the current density used). A current was continuously applied until the cell voltage reached -0.5 V (FIG. 3), at which point the lithium on the working electrode was completely stripped. The capacity when the voltage reaches −0.5 V, in this case 9.98 mAh / cm ² , is the maximum capacity of the working electrode.

Coulomb efficiency calculation Next, the Coulomb efficiency of the lithium anode was calculated using the following formula.

Here, Q ₀ is the theoretical lithium capacity of the electrode (10.2 mAh / cm ² ), Q _f is the maximum capacity of the working electrode after the deep cycling experiment (9.98 mAh / cm ² ), and Q _c is. The capacity of the cell during high rate cycling (2 mA / cm ² ), where N is the number of high rate cycles performed (51 cycles).

The Coulomb efficiency of the protective anode was therefore 98.9%.

Example 4
XPS on the surface of the protective anode
X-ray photoelectron spectroscopy (XPS) experiments were performed using the Thermo Scientific ESCALAB 250Xi instrument. The device was equipped with an electronic flood and a scanning ion gun. To prevent oxidation and contamination of the sample, the protective anode was carefully rinsed with dimethyl carbonate (DMC: DiMethyl Carbonate) and dried under an argon stream prior to characterization. The sample was transferred to the loading chamber of the instrument using a mobile glove box filled with Ar. All spectra were calibrated for 284.8 eV C1s binding energy. To quantify the atomic concentration of each element, all data were processed by Thermo Avantage software based on the Scoffield sensitivity factor. The background signal was removed by the Silly method. Typical XPS spectra of the anode surface in the regions of Li 1s, C 1s, and O 1s consistently showed that the protective layer on the anode surface was predominantly Li ₂ CO ₃ . As shown in the spectrum (see FIGS. 4-6), the reference binding energies for Li ₂ CO ₃ in the Li 1s, C 1s, and O 1s regions are 55.15 eV, 289.5 eV, and 531.5 eV, respectively. Is.

No evidence of other products such as Li ₂ O, Li ₂ O ₂ , or LiOH was observed. The standard binding energies of these products in the Li 1s region are 55.6 eV, 54.5 eV and 54.9 eV, respectively, and in the O 1s region they are 531.3 eV, 531 eV and 531 eV, respectively. These spectra show binding energies that are in good agreement with the standard binding energies of Li ₂ CO ₃ .

Element quantification results based on the surface area of the corresponding peaks of each element further support the atomic ratio of Li ₂ CO ₃ as the main product on the surface of the lithium anode.

The physical and electronic properties of Li ₂ CO ₃ provide both ionic conductivity and electronic insulation, which are two basic properties of any protective intermediate period utilized, for example in secondary lithium batteries. Is. Without being bound by theory, the ionic conductivity of the Li ₂ CO ₃ layer can allow Li ⁺ diffusion to or from the underlying anode, while the electron insulation prevents poisoning of the anode.

Example 5
Thickness-Dependant Performance of Protective Layer (or Thickness-Dependant Performance of Protective Layer)
The effect of the number of cycles performed in the anode protection process was investigated. Protected anodes were made according to Example 1, but the number of charge-discharge cycles (ie, anode protection cycles) was varied (5, 10, 15, and 20 cycles). After protection, the anode was incorporated into a lithium-air battery prepared according to Example 2. The air-filled battery was then connected to the Potentiostat (MTI Corporation) for cycling measurements. The cells were subjected to a specified number of cycles, each cycle consisting of a 1 hour charging process, where a current density of 0.1 mA / cm ² was applied, followed by a 1 hour discharging process. In-situ measurements of voltage as a function of time and capacity were recorded.

FIG. 7 shows the cycle life of a lithium-air battery and the first cycle polarization gap as a function of the number of protection cycles (correlated to the thickness of the protection layer). Battery cycle life has been shown to be approximately 60 cycles after 5 anode protection cycles and 800 cycles after 10 anode protection cycles. In the Li-air battery polarization gap as a function of the number of anode protection cycles, the opposite trend was observed, with the smallest polarization gap observed in 5 anode protection cycles. The polarization gap for the first cycle without anode protection was 1.366V. After 5 protection cycles, the potential gap dropped to 0.4933V for the battery containing the anode. Beyond 5 protection cycles, the first cycle polarization gap increased up to 20 cycles as the number of anode protection cycles increased.

These results suggest that for lithium-air batteries, the optimum number of anode protection steps is about 10 cycles.

Example 6
EIS characterization (or EIS characterization) of a lithium-air battery with a protective anode
To investigate the effect of anode protective layer thickness on cell stability and efficiency, protected anodes were made according to Example 1, but with varying numbers of anode protection cycles (5, 10, and 15 cycles). It was incorporated into a lithium-air battery prepared according to 2. Each electrochemical impedance spectroscopy (EIS) experiment uses a new cathode with a known loading of catalyst and the same electrolyte to ensure an independent study of the electrochemical properties of the protected anode in the system. Avoided contamination or external resistance. The battery cell was connected to a potentiostat (Volta Lab PGZ 100), and measurements were performed at an overvoltage of 700 mV in the frequency range of 10 Hz to 100 kHz.

FIG. 8 shows the EIS results regarding the number of anode protection cycles. The charge transfer resistance ( _Rct ) of the anode after 10 protection cycles was about 550 kiloohms, but after 5 and 15 cycles it was about 160 kiloohms and about 1350 kiloohms, respectively. The charge transfer resistance to the unprotected anode was 30 kiloohms.

Without being bound by theory, the increase in cell resistance may be due to the presence of Li ₂ CO ₃ on the surface of the anode. The thicker the protective layer, the greater the charge transfer resistance in the cell. The thickness of the protective layer after the 5 anode protection cycle was not sufficient to protect the lithium-air battery over a long period of time, but the 15 anode protection cycle made the resistance in the cell too high, such as It is considered unsuitable for batteries.

Based on these results, the anode after 10 protection cycles showed the best electrochemical performance.

［式中、Ｒ _１ 、Ｒ _２ およびＲ _３ は、水素、直鎖脂肪族Ｃ _１ ～Ｃ _６ 基、分岐脂肪族Ｃ _１ ～Ｃ _６ 基および環状脂肪族Ｃ _１ ～Ｃ _６ 基からなる群から独立して選択される］
を有する、態様４７に記載の方法。
（態様５０）
Ｒ _２ が、水素であり、
Ｒ _１ およびＲ _３ が、直鎖または分岐のＣ _１ ～Ｃ _４ アルキルから独立して選択される、
態様４９に記載の方法。
（態様５１）
前記アニオンが、Ｃ _１ ～Ｃ _６ アルキルスルフェート、トシレート、メタンスルホネート、ビス（トリフルオロメチルスルホニル）イミド、ヘキサフルオロホスフェート、テトラフルオロボレート、トリフレート、ハライド、カルバメートまたはスルファメートである、態様４７～５０のいずれか１項に記載の方法。
（態様５２）
前記イオン液体が、１－エチル－３－メチルイミダゾリウムテトラフルオロボレートである、態様４６～５１のいずれか１項に記載の方法。
（態様５３）
前記電解質が、少なくとも５０重量％のイオン液体を含む、態様４６～５２のいずれか１項に記載の方法。
（態様５４）
前記電解質が、少なくとも９０重量％のイオン液体を含む、態様４６～５２のいずれか１項に記載の方法。
（態様５５）
前記電解質が、水および非イオン性の液体の有機溶媒を実質的に含まない、態様１～５４のいずれか１項に記載の方法。
（態様５６）
前記電解質が、非プロトン性の有機溶媒を含む、態様１～５４のいずれか１項に記載の方法。
（態様５７）
前記溶媒が、エーテルである、態様５６に記載の方法。
（態様５８）
前記溶媒が、テトラエチレングリコールジメチルエーテル、ジメトキシエタンまたはジメチルスルホキシドである、態様５６に記載の方法。
（態様５９）
１回以上の放電－充電サイクルの後、前記電気化学セルから、前記保護アノードを取り除くこと、および
電池を構成すること
をさらに含み、
前記電池は、
前記保護アノード、
カソード、および
前記アノードと接触し、必要に応じて、前記アノードの金属とも接触する電解質
を含む、態様１～５８のいずれか１項に記載の方法。
（態様６０）
前記電池のカソードが、遷移金属ジカルコゲナイドを含まない、態様５９に記載の方法。
（態様６１）
態様１～５８のいずれか１項に記載の方法に従って製造される保護アノード。
（態様６２）
保護アノードであって、該保護アノードは、保護層を含み、該保護層は、アノードに配置され、該アノードは、リチウム金属を含み、前記保護層は、Ｌｉ _２ ＣＯ _３ を含み、その量は、前記保護層の少なくとも５０原子％である、保護アノード。
（態様６３）
態様６１または態様６２に記載の保護アノード、
カソード、および
前記アノードと接触し、必要に応じて、前記アノードの金属とも接触する電解質
を含む、電池。
（態様６４）
金属－空気の電池として構成されている、態様６３に記載の電池。
（態様６５）
前記カソードが、少なくとも１つの遷移金属ジカルコゲナイドを含む、態様６４に記載の金属－空気の電池。
（態様６６）
前記電解質が、少なくとも５０重量％のイオン液体を含む、態様６４または６５に記載の金属－空気の電池。
（態様６７）
金属－イオンの電池として構成されている、態様６３に記載の電池。
（態様６８）
金属－硫黄の電池として構成されている、態様６３に記載の電池。
（態様６９）
前記カソードが、遷移金属ジカルコゲナイドを含まない、態様６４、６７および６８のいずれか１項に記載の電池。
Example 7
SEM characterization (or SEM characterization) of the protective anode surface
The surface structure and morphology of the protective anode was examined through a scanning electron microscope (SEM). Protected lithium anodes made according to Example 1 were characterized. SEM images were acquired at an acceleration voltage of (EHT) 10 kV with a lens magnification of 15 kX and an acceleration voltage of (EHT) 10 kV with a lens magnification of 25 kX. An SEM image of the surface of the protective anode (see FIG. 9) shows the formation of rod-shaped products consistent with Li ₂ CO ₃ species.
The disclosure of the present specification may include the following aspects.
(Aspect 1)
A method for manufacturing a protective anode, which method is:
Providing electrochemical cells, and
Performing a discharge-charge cycle
Including
The electrochemical cell is
Cathode containing at least one transition metal dicalcogenide,
Anode containing metal,
The transition metal dichalcogenide of the cathode and the electrolyte in contact with the metal of the anode, and
Carbon dioxide dissolved in the electrolyte
Including
The discharge-charge cycle is
Discharging the electrochemical cell and
Applying a voltage across the anode and the cathode for a time sufficient to charge the electrochemical cell.
Including
In that method
The electrochemical cell is substantially free of water and is free of water.
One or more species have been deposited on the anode, the species being formed in the discharge-charging cycle and dissolved in the electrolyte.
Method.
(Aspect 2)
The method of aspect 1, wherein the electrochemical cell contains less than about 5% by weight of water of the electrolyte.
(Aspect 3)
The method of aspect 1, wherein the electrochemical cell contains less than about 2% by weight of water of the electrolyte.
(Aspect 4)
The method of aspect 1, wherein the electrochemical cell contains less than about 1% by weight of water of the electrolyte.
(Aspect 5)
The method according to any one of aspects 1 to 4, wherein the electrochemical cell is substantially free of H ₂ and O ₂ .
(Aspect 6)
5. The method of aspect 5 , wherein the electrochemical cell comprises an amount of H ₂ that is less than 5% by weight of the electrolyte.
(Aspect 7)
5. The method of aspect 5, wherein the electrochemical cell comprises an amount of H ₂ that is less than 2% by weight of the electrolyte.
(Aspect 8)
The method according to any one of aspects 5 to 7 , wherein the electrochemical cell contains less than 5% by weight of O ₂ of the electrolyte.
(Aspect 9)
The method according to any one of aspects 5 to 7 , wherein the electrochemical cell contains less than 2% by weight of O ₂ of the electrolyte.
(Aspect 10)
The method according to any one of aspects 5 to 9, wherein the electrochemical cell contains H ₂ and O ₂ and the total amount thereof is less than about 10% by weight of the electrolyte.
(Aspect 11)
The method of any one of aspects 1-10, further comprising performing one or more additional discharge-charge cycles.
(Aspect 12)
11. The method of aspect 11, wherein the total number of discharge-charge cycles is 2-25.
(Aspect 13)
11. The method of aspect 11, wherein the total number of discharge-charge cycles is 5-15.
(Aspect 14)
The method according to any one of aspects 1 to 13, wherein the voltage is in the range of about 1 V to about 5 V.
(Aspect 15)
The method according to any one of aspects 1 to 14, wherein the anode is basically made of metal.
(Aspect 16)
The method according to any one of aspects 1 to 15, wherein the metal of the anode is lithium, magnesium, zinc or aluminum.
(Aspect 17)
The method according to any one of aspects 1 to 15, wherein the metal of the anode is lithium.
(Aspect 18)
The method according to any one of aspects 1 to 17, wherein the electrolyte contains a metal ion.
(Aspect 19)
18. The method of aspect 18, wherein the metal ion is a lithium ion, a magnesium ion, a zinc ion or an aluminum ion.
(Aspect 20)
18. The method of aspect 18, wherein the metal ion is a lithium ion.
(Aspect 21)
The method according to any one of aspects 18 to 20, wherein the metal ion is present in the electrolyte at a concentration in the range of about 0.005 M to about 5 M.
(Aspect 22)
The method according to any one of aspects 18 to 20, wherein the metal ion is present in the electrolyte at a concentration in the range of about 0.01 M to about 1 M.
(Aspect 23)
The method according to any one of aspects 18 to 20, wherein the metal ion is present in the electrolyte at a concentration in the range of about 0.02 to about 0.5 M.
(Aspect 24)
The method according to any one of aspects 18 to 23, wherein the metal of the anode and the element of the metal ion are the same.
(Aspect 25)
The method according to any one of aspects 1 to 24, wherein the carbon dioxide is present in the electrolyte at a concentration of at least about 5% of the carbon dioxide saturation concentration in the electrolyte.
(Aspect 26)
The method according to any one of aspects 1 to 24, wherein the carbon dioxide is present in the electrolyte at a concentration of at least about 25% of the carbon dioxide saturation concentration in the electrolyte.
(Aspect 27)
The method according to any one of aspects 1 to 24, wherein the carbon dioxide is present in the electrolyte at a concentration of at least about 50% of the carbon dioxide saturation concentration in the electrolyte.
(Aspect 28)
The method according to any one of aspects 1 to 27, wherein the material of the transition metal dichalcogenide-containing cathode contains at least 50% by weight of the transition metal dichalcogenide.
(Aspect 29)
The method according to any one of aspects 1-28, wherein the cathode comprises at least one transition metal dicalcogenide disposed in a porous member or current collector.
(Aspect 30)
The method according to any one of aspects 1-28, wherein the cathode comprises at least one transition metal dicalcogenide disposed in a porous carbon member.
(Aspect 31)
29. The method of aspect 29 or 30, wherein the porous member is conductive.
(Aspect 32)
Each transition metal dicalcogenide is TiX ₂ , VX ₂ , CrX ₂ , ZrX ₂ , NbX ₂ , MoX ₂ , HfX ₂ , WX ₂ , TaX ₂ , TcX ₂ or ReX ₂ .
Each X is independently S, Se or Te or a combination thereof.
The method according to any one of aspects 1 to 31.
(Aspect 33)
Each transition metal dicalcogenide is TiX ₂ , MoX ₂ or WX ₂ .
Each X is independently S, Se or Te or a combination thereof.
The method according to any one of aspects 1 to 31.
(Aspect 34)
The method according to any one of aspects 1-31, wherein each transition metal dicalcogenide is TiS ₂ , TiSe ₂ , MoS ₂ , MoSe ₂ , WS ₂ or WSe ₂ .
(Aspect 35)
The method according to any one of aspects 1-31, wherein each transition metal dicalcogenide is TiS ₂ , MoS ₂ or WS ₂ .
(Aspect 36)
The method according to any one of aspects 1-31, wherein each transition metal dicalcogenide is MoS ₂ or MoSe ₂ .
(Aspect 37)
The method according to any one of aspects 1-31, wherein each transition metal dicalcogenide is MoS ₂ .
(Aspect 38)
The method according to any one of aspects 1-37, wherein each transition metal dicalcogenide is in the form of nanoparticles.
(Aspect 39)
38. The method of aspect 38, wherein the transition metal dicalcogenide nanoparticles have an average size in the range of about 1 nm to about 1000 nm.
(Aspect 40)
The method according to any one of aspects 1-37, wherein each transition metal dicalcogenide is in the form of nanoflakes.
(Aspect 41)
40. The method of aspect 40, wherein the transition metal dicalcogenide nanoflakes have an average size in the range of about 1 nm to about 400 nm.
(Aspect 42)
Embodiments of the transition metal dicalcogenide nanoflakes having an average thickness in the range of about 1 nm to about 100 nm, average dimensions along the main surface of about 50 nm to about 10 μm, and an aspect ratio of at least about 5: 1. 40.
(Aspect 43)
The method according to any one of aspects 1-37, wherein each transition metal dicalcogenide is in the form of nanosheets or nanoribbons.
(Aspect 44)
43. The method of aspect 43, wherein the transition metal dicalcogenide nanosheet or nanoribbon has an average size in the range of about 1 nm to about 400 nm.
(Aspect 45)
The method according to any one of aspects 1-37, wherein each transition metal dicalcogenide is in bulk form.
(Aspect 46)
The method according to any one of aspects 1 to 45, wherein the electrolyte comprises an ionic liquid.
(Aspect 47)
The ionic liquid
With cations selected from imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium, choline, sulfonium, prolinate and methioninate,
With anions
46. The method of aspect 46.
(Aspect 48)
47. The method of aspect 47, wherein the cation is an imidazolium cation.
(Aspect 49)
The cation is an imidazolium cation, and the imidazolium cation has the following formula:

[In the formula, R ₁ , R ₂ and R ₃ consist of hydrogen, linear aliphatic C ₁ to C ₆ groups, branched aliphatic C ₁ to C ₆ groups, and cyclic aliphatic C ₁ to C ₆ groups. Selected independently]
47. The method of aspect 47.
(Aspect 50)
R ₂ is hydrogen,
R ₁ and R ₃ are selected independently of the linear or branched C ₁ to C ₄ alkyl.
The method according to aspect 49.
(Aspect 51)
Aspects _47-50 , wherein the anion is C1 _- C6 alkyl sulphate, tosylate, methanesulfonate, bis (trifluoromethylsulfonyl) imide, hexafluorophosphate, tetrafluoroborate, triflate, halide, carbamate or sulfamate. The method according to any one of the above.
(Aspect 52)
The method according to any one of aspects 46 to 51, wherein the ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate.
(Aspect 53)
The method according to any one of aspects 46 to 52, wherein the electrolyte comprises at least 50% by weight of an ionic liquid.
(Aspect 54)
The method according to any one of aspects 46 to 52, wherein the electrolyte comprises at least 90% by weight of an ionic liquid.
(Aspect 55)
The method according to any one of aspects 1 to 54, wherein the electrolyte is substantially free of water and a nonionic liquid organic solvent.
(Aspect 56)
The method according to any one of aspects 1 to 54, wherein the electrolyte comprises an aprotic organic solvent.
(Aspect 57)
56. The method of aspect 56, wherein the solvent is ether.
(Aspect 58)
56. The method of aspect 56, wherein the solvent is tetraethylene glycol dimethyl ether, dimethoxyethane or dimethyl sulfoxide.
(Aspect 59)
After one or more discharge-charge cycles, the protective anode is removed from the electrochemical cell, and
Configure the battery
Including
The battery is
The protective anode,
Cathode, and
An electrolyte that contacts the anode and, if necessary, the metal of the anode.
The method according to any one of aspects 1 to 58, comprising.
(Aspect 60)
59. The method of aspect 59, wherein the cathode of the battery does not contain a transition metal dicalcogenide.
(Aspect 61)
A protective anode manufactured according to the method according to any one of aspects 1 to 58.
(Aspect 62)
A protective anode, the protective anode comprising a protective layer, the protective layer being disposed on the anode, the anode comprising a lithium metal, said protective layer comprising Li ₂ CO ₃ in an amount thereof. A protective anode that is at least 50 atomic% of the protective layer.
(Aspect 63)
The protective anode according to aspect 61 or aspect 62,
Cathode, and
An electrolyte that contacts the anode and, if necessary, the metal of the anode.
Including batteries.
(Aspect 64)
13. The battery of aspect 63, configured as a metal-air battery.
(Aspect 65)
The metal-air battery of embodiment 64, wherein the cathode comprises at least one transition metal dichalcogenide.
(Aspect 66)
The metal-air battery according to aspect 64 or 65, wherein the electrolyte comprises at least 50% by weight of an ionic liquid.
(Aspect 67)
The battery according to aspect 63, which is configured as a metal-ion battery.
(Aspect 68)
The battery according to aspect 63, which is configured as a metal-sulfur battery.
(Aspect 69)
The battery according to any one of aspects 64, 67 and 68, wherein the cathode does not contain a transition metal dicalcogenide.

Claims (18)

A protective anode, wherein the protective anode comprises a protective layer, the protective layer is disposed on the anode, the anode comprises lithium , the protective layer comprises Li ₂ CO ₃ , and the amount thereof is said. It is at least 50 atomic% of the protective layer, the C 1s region of the X-ray photoelectron spectrum of the protective layer shows a CC peak, and the Li 1s region of the X-ray photoelectron spectrum of the protective layer has a single peak. Shown , protective anode. The protective anode according to claim 1, wherein the only lithium salt observed in the protective layer by X-ray photoelectron spectroscopy is Li ₂ CO ₃ . The protective anode according to claim 1 or 2, wherein the protective layer has a thickness in the range of 5 nm to 40 μm. The protective anode according to any one of claims 1 to 3, which is in contact with an electrolyte containing an ionic liquid. The protected anode according to claim 4, wherein the electrolyte further comprises dimethyl sulfoxide. A protective anode manufactured according to a method comprising providing an electrochemical cell and performing a discharge-charge cycle.
The electrochemical cell is
Cathode containing at least one transition metal dicalcogenide,
Anode containing metal,
It contains the transition metal dicalcogenide of the cathode, the electrolyte in contact with the metal of the anode, and carbon dioxide dissolved in the electrolyte.
The discharge-charge cycle is
Includes discharging the electrochemical cell and applying a voltage across the anode and cathode for a time sufficient to charge the electrochemical cell.
The carbon dioxide is present in the electrolyte at a concentration of at least 25% of the carbon dioxide saturation concentration in the electrolyte.
The electrochemical cell is substantially free of water and is free of water.
One or more species are deposited on the anode to form the protective layer, the species are formed in the discharge-charge cycle and dissolved in the electrolyte.
The protective anode according to any one of claims 1 to 3. The protected anode according to claim 6 , wherein in the method, the electrochemical cell contains less than 1% by weight of water of the electrolyte. The protected anode according to claim 6 or 7 , wherein in the method, the electrochemical cell comprises H ₂ in an amount less than 2% by weight of the electrolyte and O ₂ in an amount less than 2% by weight of the electrolyte. .. The protective anode according to any one of claims 6 to 8 , wherein in the method, the material of the transition metal dichalcogenide-containing cathode contains at least 50% by weight of the transition metal dichalcogenide. The protective anode according to any one of claims 6 to 9 , wherein in the method, each transition metal dicalcogenide is in the form of nanoflakes, nanosheets or nanoribbons. The protected anode according to any one of claims 6 to 10 , wherein in the method, the electrolyte comprises at least 10% ionic liquid. The protected anode according to any one of claims 6 to 11, wherein the total number of anode protection cycles as a discharge-charge cycle is 5 to 15. The protective anode according to any one of claims 1 to 12 .
A battery comprising a cathode and an electrolyte that contacts the anode and optionally the metal of the anode. 13. The battery of claim 13 , configured as a metal-air battery, a metal-ion battery or a metal-sulfur battery. 13. The battery according to claim 13 , wherein the cathode does not contain a transition metal dicalcogenide . A method for manufacturing a protective anode, which method is:
Includes providing electrochemical cells and performing a discharge-charge cycle.
The electrochemical cell is
Cathode containing at least one transition metal dicalcogenide,
Anode containing lithium metal,
It contains the transition metal dicalcogenide of the cathode, the electrolyte in contact with the metal of the anode, and carbon dioxide dissolved in the electrolyte.
The discharge-charge cycle is
Includes discharging the electrochemical cell and applying a voltage across the anode and cathode for a time sufficient to charge the electrochemical cell.
The carbon dioxide is present in the electrolyte at a concentration of at least 25% of the carbon dioxide saturation concentration in the electrolyte.
In that method
The electrochemical cell is substantially free of water and is free of water.
One or more species have been deposited on the anode, the species being formed in the discharge-charging cycle and dissolved in the electrolyte.
Method. 16. The method of claim 16 , further comprising removing the protective anode from the electrochemical cell after one or more discharge-charge cycles. Including further constituting the battery,
The battery is
The protective anode,
Contains an electrolyte that contacts the cathode and, optionally, the metal of the anode.
In this method, if necessary,
(A) the battery is configured as a metal-air battery, a metal-ion battery or a metal-sulfur battery, and / or (b) the cathode is free of transition metal dicalcogenides.
17. The method of claim 17 .

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